Phosphated polyols and process for making same

ABSTRACT

A novel phosphated polyol is provided which is used in conjunction with aminoplast resins to provide improved soil release particles to cellulosic fibers and blends of cellulosic fibers with polyester fibers having durable press or wash and wear characteristics.

United States Patent 1151 3,692,880 Doerr et al. [4 1 Sept. 19, 1972 54]PHOSPHATED POLYOLS AND [56] References Cited 72 f g MAKING SAME UNITEDSTATES PATENTS t h L.

l 1 zf ggf'g g %gff 3,275,667 9/1966 Bohnunek ..260/929 x Assignee= OlinCorporation Primary Examiner-LewisGotts 22 Fil d; M 4 1970 AssistantExaminer-Anton H. Sutto' v Attorney-Gordon D. Byrkit, Donald F.Clements, [211 APPI- 341606 Thomas P. ODay and F. A. lskander 52 US. Cl..260/929, 117/151 L, 117/161, 1571 ABSTRACT 260/676 260/70 260/920 gigA novel phosphated polyol is provided which is used 51 Int. Cl. ..c0719/08 D06m 1/100 with amimplas resins Pmvide 58 Field of Search..260/920, 929, 980, 928 Pwved release Particles cellulsi fibers andblends of cellulosic fibers with polyester fibers having durable pressor wash and wear characteristics.

4 Claims, No Drawings .PHOSPHATED POLYOLSA'ND PROCESSFOR MAKINGSAME Thisinvention relates to novel textile treating'compositions, the methodofpreparing and applying such compositions and to textile-materialstreated therewith. More specifically-,the invention relates tocompositions and textile treatments which provide improved soil releaseproperties to textiles.

Cellulosic fibers, including cotton, linen, jute, flax and regeneratedcellulose fibers, including viscose rayon, in the form of staple, yarnand fabrics have generally satisfactory soil release properties.

The term soil release refers to .the ability of the fiberto be washed toremove soil and particularly oily materials in contactwith said fibers.The present invention promotes the removal of soil from fibers .andrenders fabrics more amenable to cleansingby washmg.

A further feature of the present invention is the prevention of soilredeposition from the wash water. During washing and rinsing, the soilhas a tendency to redeposit on the fibers from'the wash water or rinsewater. The soil release ability of fibers treated according to thepresent invention also prevents redeposition of soil removed in thewashing.

The introduction of blends of cotton withsynthetic fibers hasaggravatedthe problem of soil release and redeposition. The syntheticfibers, particularly the polyester fibers, for example, those preparedfrom poly(ethylene terephthalate), have many desirableproperties whichhave made them commercially acceptable for many end uses,'both alone andin variouscombinations with natural fibers. Howeventhe soil releaseproperties of the polyester fibers are much poorer than those of thecellulosic fibers. The polyester fibers are hydrophobic rather thanhydrophilic. They attract and hold the soil more tenaciously thancellulosic fibers and hinder the ingress of water necessary 'forcleaning the fabric.

The problem of soil release and redeposition has been further compoundedby-durable press and washand-wear treatments which render the cellulosicfibers in textiles .and blends less hydrophilic. These finishingtreatments usually consist of impregnating and reacting the cellulosicfibers with aminoplast resins having N- methylol groups, e.g.,urea-formaldehyde resins, cyclic urea-formaldehyde resins, especiallydihydroxy dimethylol ethyleneurea resins. The fibers subjected to suchtreatments retain the soil more tenaciously than the untreatedcellulosic fibers, lose much of their soil release properties and aremore subject to redeposition of soil. Oily soils accepted and retainedby garments of these fibers, when worn, are difficult to remove innormal washing machine operations. Even relatively clean garmentscontaining these treated fibers tend to pickup soil from the dirty washwater. As a result, oily soil spots are never completely removed fromthese garments by washing. Repeated washings intensify the effects ofsoil pick-up from the dirty wash water with increasing overall grey oryellow discoloration. Eventually the garment becomes unsightly before itis worn out.

Soil release agents presently available do not provide fibers withadequate levels of initial and durable soil release properties when thefibers have been subjected to durable press or wash-and wear finishing.

Present soil release agents based on'polymeric derivatives of acrylicacid are disclosed, for example, in

'terpolymer and US. Pat. No. 3,377,249 directed to a process in whichthe active soil release agent is a copolymer of ethyl acrylate andacrylic acid in a :30

ratio. Problems which still remain when known soil release agentsareused with cellulosic textiles, including blends with polyesters,which have been finished with aminoplast resins include:

l. Unsatisfactory initial soil release efiect.

2.'Poor durabilityof soil release properties to repeated washings.

3. Poor compatibility with the magnesium chloride or zinc nitratecatalysts commonly used in aminoplast resin finishing compositions.

4. Require a two-bath process instead of a single bath application forbest results.

5. Acrylate emulsions tend to precipitate on standing. Some have poorfreeze-thaw stability.

6. Acrylate soil release emulsions tend to form gritty deposits onfabric pad rolls during application which causes problems when pickedoff by the fabric.

The present invention isprimarily directed to the treatment ofcellulosic fabrics and to fabrics containing a substantial portion ofsynthetic polyester fibers. These fibersare generally formed intofabrics which are knitted, woven or non-woven. However, the advantagesof this invention can be acheived by treating the fibers,-yarns, orthreads employed to produce these fabrics. Moreover, and morespecifically, the process of the present invention is preferably usedfor treating textile materials containingcellulosic fibers or blends ofpolyester and cellulosic fibers to confer durable press or minimum carecharacteristics and improved soil release properties. The fabrics aresuitably formed from a mixture of polyester, e.g., poly(ethyleneterephthalate) fibers and cotton or rayon fibers. Textile materialscontaining only cellulosic fibers are also within theiscopeof thepresentinvention.

Surprisingly, it has now been discovered that the above mentionedproblems and deficiencies are substantially eliminated by combiningphosphated polyoxyalkylene ester of phosphoric acid with an aminoplasttextile resin and an aminoplast resin catalyst, applying the mixture tothe textile and subjecting the treated textile to resin curingconditions. The invention contemplates the phosphated product, thefinishing composition combining the phosphated product and theaminoplast resin, catalyzed and uncatalyzed, the

process of treating fibers with the treating composition and the fibersand textiles thus treated.

Advantages of the present invention are:

1. An improved level of initial soil release effect on treated fabric.

2. An improved level of durable soil release effect on treated fabricafter multiple washings.

3. Improved compatibility with the magnesium chloride and zinc nitratetextile resin catalysts commonly used in aminoplast textile resinformulations.

4. A single bath process that increases rate of production and is moreeconomical than a twobath process.

5. A completely homogeneous water-soluble finishing composition notsubject to separation or freeze-thaw instability.

6. No undesirable product build-up on fabric pad rolls duringapplication.

The phosphated soil release agent is prepared by l) oxyalkylating 100percent phosphoric acid with two to moles of alkylene oxide, suitablypropylene oxide or mixtures with up to 50 percent by weight of ethyleneoxide to form a polyol and (2) reacting the resulting polyol withphosphoric acid or phosphoric anhydride.

Minor amounts, from 2 to 25 percent by weight of the alkylene oxidemixture is suitably other alkylene oxides of two to four carbons, forexample, alphaor beta-butylene oxide, trichlorobutylene oxides, glycidoland epichlorohydrin. The oxides are also suitably reacted with 100percent phosphoric acid in block type as well as random type polymers.

The oxyalkylated phosphoric ester (polyol) is suitably phosphated withphosphoric anhydride or phosphoric acid containing at least 85 percent HPO Suitable molar ratios of polyol per phosphorus atom in thephosphating agent are from 0.5:1 to 2.2:] and preferably from 0.75:1 to1.521. The preferred phosphating agent is phosphoric anhydride whichgives the most effective and durable soil release agent.

The reaction of the polyol with the phosphating agent is carried out attemperatures up to 150 C. under pressures of atmospheric or below, e.g.,from 5 to 780 mm. Thorough mixing of the polyol with the phosphatingagent, particularly phosphoric anhydride, is advantageous to providesufficient initial reaction to solubilize most of the phosphoricanhydride in the polyol, sufficient reaction time and temperature toessentially complete the reaction, followed by filtration to remove anysmall amounts of undissolved solids. The rate of reaction is temperaturedependent but it proceeds even at 20 C. or below. The rate of reactionis accelerated by increasing the temperature, but color formationincreases above about 70 C. The temperature range is suitably from 0 C.to 150 C. with very long reaction time at low temperatures and veryshort reaction time at high temperatures. The preferred range is 3080 C.for minutes to 1 week.

The resulting phosphated polyols are clear, light amber colored, highlyviscous liquids at room temperature. Yields are about 90 to 95 percent.Hydroxyl numbers vary from about 140 to 190. The acid numbers showvalues of about 190 and 250 (two breaks). The pH of a percent solutionin distilled water is from 0.5 to 1.0. Viscosity at 70 C. is from 20,000to 40,000 CPS.

Th'e phosphated polyol thus prepared is used in conjunction with anaminoplast resin composition for treating textiles. Suitable resins arethe well-known, commercially available aminoplasts, for example, N-methylol compositions based on urea-formaldehyde, cyclicurea-formaldehyde and especially dihydroxy dimethylol ethyleneurearesins. Catalysts usually added to these resins are metal salts of theformula MX where M is magnesium or zinc and X is chloride or nitrate,particularly, magnesium chloride or zinc nitrate. Usually from 1 to 15percent of the catalyst, based on the weight of the resin is suitable.

The proportion of phosphated polyol added to the aminoplast compositionis usually about 2 to 10 percent based on the total weight of theformulation. In use, the mixture of phosphated polyol and aminoplast,including catalyst, is applied to the fiber or textile to be treated andcured under conditions usual for applying and curing the aminoplastfinishing compositions, that is, at temperatures of about 300 to 400 F.for 0.1 to 15 minutes.

EXAMPLE I A. Preparation of percent-Phosphoric Acid Initiator for thepolyol was 100 percent phosphoric acid prepared from commercial percentphosphor- I formed of 304 stainless steel fitted with an agitator andequipped to add the alkylene oxide below the surface of the liquid inthe reactor. Both acid feed and oxide feed were introduced into thereactor under nitrogen pressure through flow meters and check valves.

The reactor initially contained 12 pounds of a finished product from aprevious batch. The oxide used was a mixture of propylene oxide andethylene oxide in a ratio of 90:10 by weight. During a period of about28 hours, the acid and oxide were introduced using a higher proportionof the acid, .based on the total to be introduced, than the proportionof oxide. The molar ratio of oxide to acid initially was 1.44:1 whichrose to 4.33:1 in the final product. During the addition of thereactant, the temperature, initially at 1 0 C. rose to 70 C. and thepressure varied from 16 to 27 psig. The total weight of acid introducedwas 1 17 pounds and the total oxide was 507 pounds. Subsequently at 70C., an additional 136 pounds of the oxide mixture was introduced in fourportions with a holding period of 2 to 4 hours at 70 C. after eachaddition. The final pH was 5.8. After completion of the reaction,unreacted oxide was stripped by heating the mixture for 3 hours at 75 C.under pressures from 10 to 25 mm. The product amounted to 631 pounds or79.3 percent based on the material charged.

C. Reaction of Polyol with Phosphoric Anhydride A portion of parts byweight of the polyol prepared in Example LB. having a hydroxyl number of303 and a molecular weight of 555.5 was charged to a well-stirredreactor followed by 42 grams of phosphoric anhydride. The mixture wasmaintained at 20 to 30 C. for 2 hours by cooling and then thetemperature rose to 60 C. during 3 hours. The mixture was maintainedwith stirring at atmospheric pressure and at 60 C. for an additional 7.5hours, filtered and cooled.

D. Formulation Preparation Five grams of the product from Example LC.was weighed into a 250 ml. breaker and dissolved in 19 grams ofdistilled water. The pH of the aqueous solution was adjusted to 7.0 on aBeckman Glass Electrode pH Meter by the slow addition of 10 percentaqueous sodium hydroxide solution (7 g.) using good agitation. To theneutralized solution was added 13 grams of Permafresh LF," a dimethylolcyclic urea compound, 1

gram of Polymel CC, a polyethylene emulsion softener and 5 grams of 20percent by weight ageuous magnesium chloride solution. The finalformulation had a pH of5.9. E. Formulation Application A 5 X 8 inchesswatch of 65/35 Dacron/cotton shirting fabric was thoroughly wetted intheformulation prepared in Example 1.D. Excess solution was removed fromfabric by passing the open width through pressurized rubber squeezerolls to give approximately 60 percent wet pick-up of the formulation onthe dry weight of the goods. The impregnated fabric was dried at 110 to120 C. for 90 seconds and then cured at 1591 6 1 C. for 180 seconds. IF. Soil Release Evaluation I The cured fabric, after 30 minutes atambient temperature and humidity, was soiled with 10 drops of dirtymotor oil centrally distributed over a 2 to 4 square inch area. The oilwas allowed to soak into the fabric for 30 minutes and then it waswashed in a Tergotometer at 50-55 C. for 20 minutes using 1.5 grams ofTide in 1 liter of water. The washed fabric was rinsed in warm water anddried on a line. The dried fabric was rated for soil release visually byplacing the sample on a white cardboard background and observing thecolor intensity of any remaining dirty motor oil soil. The fabric ofthis example gave complete soil release of the dirty motor oil. The sametype of fabric finished with 10 percent Rhoplex SR-488, a commercialacrylic type soil release agent, in a conventional two-bath applicationand soiled and washed in the previously described manner, did not givecomplete soil release of dirty motor oil. The soiled area was clearlyvisible after washing. Other portions of the same fabrics-washed priorto soiling still show the superior soil release properties of theproduct of this invention applied in a single bath over Rhoplex SR-488applied by a two-bath application.

Reflectance was also measured after soiling with dirty motor oil andwashing, as described above, using a Photovolt reflectometer with a bluefilter. The reflectance of the treated cloth was 76 initially aftersoiling and one washing. Another treated swatch was washed 5 times,soiled and washed again. Reflectance was 63, showing excellentdurability.

EXAMPLE II A. Preparation of Polyol Propylene oxide and 100 percentphosphoric acid, prepared as described in Example I.A. were introducedinto a nitrogen padded reactor cooled externally with ice water. Areflux condenser cooled with dry ice was provided. The mixture wasvigorously stirred. The feed of propylene oxide was started first and aweight ratio of propylene oxide to phosphoric acid of at least 5:] wasmaintained. The rates of addition of acid and oxides were adjusted tomaintain the reaction temperature at 20 to 30 C. During 2 hours, a totalof 50 grams of 100 percent phosphoric acid and 250 grams of propyleneoxide was introduced. Finally the reaction mixture was stirred at 25 to30 C. for 6 hours. The product amounted to 295 grams.

The reaction mixture was purged with a stream of dry nitrogen andrefluxed for 4 hours at 54 C. then exmm. and the temperature was raisedto C. during a period of 0.65 hours. The reaction mixture was maintainedat that temperature for a total of 8 hours. The

mixture was filtered and cooled. It mounted to 160 grams or about 70percent based on the materials charged.

The product was formulated and applied to Dacroncotton fabric. asdescribed in Example I. The reflectance was measured using a Photovoltreflectometer' with a blue filter. The reflectance for the treated clothafter soiling and washing was 75. Another treated swatch was washed 5times, soiled and washed again. Reflectance was 61, showing excellentdurabili- EXAMPLE III A. Preparation of 100 percent Phosphoric AcidCr'ystallized 100 percent phosphoric acid was obtained by cooling 100percent phosphoric acid, prepared as described in Example I.A., with dryice to start crystallization and then holding the mixture at 35 C. forseveral hours. The crystals were filtered from the liquor. B.Preparation of Polyol To 50 ml. of a mixture of propylene oxide andethylene oxide in a weight ratio of :10 was added, during a period of1.5 hours, a total of 50 grams of melted, previously crystallizedpercent phosphoric acid, prepared as described in Example 1lI.A-., and250 grams of oxide mixture, maintaining the weight ratio of oxide toacid between 5:1 and 6:1. A reflux condenser cooled with dry iceprevented the escape of alltylene oxide. After the addition wascomplete, the reaction mixture was maintained at 20 to 30 C. for 2 hoursand then stood over night. Subsequently, the reaction mixture was heatedduring a period of 4 hours until the reflux temperature reached 70 C.where it was maintained for 2 more hours. Finally the product wasstripped for 2 hours at 70 C. under 10 mm. pressure. The yield ofphosphated polyol was 244 grams. C. Reaction of Polyol with PhosphoricAnhydride To 190 grams of the product of Example II1.B., maintainedunder nitrogen, 42 grams of phosphoric anhydride was added at 20 C. withvigorous agitation. After the addition was complete, the mixture wasstirred under nitrogen at 20 C. for 1 hour. The temperature was thengradually raised to 70 C., reducing the pressure to 10 mm. The mixturewas maintained at this pressure with stirring for 8 hours. The productwas filtered, yielding grams or 73 percent based on the materialscharged.

Formulated, applied and tested as described in Example 1, thereflectance of the Dacron-cotton was initially 74 and after fivewashings was 60.

EXAMPLE IV A. Preparation of Polyol The polyol was prepared from 50grams of 105 percent phosphoric acid and 250 grams of propylene oxidereacted as described in Example 111.3. Total reaction time at 70 C. was2 hours. The phosphated polyol product amounted to 232 grams or 77percent based on the starting material.

B. Reaction of Polyol with Phosphoric Anhydride A mixture of 190 gramsof the product of Example WA. and 40 grams of phosphoric anhydride wasreacted as described in Example ILB. at temperatures up to 70 C. for aperiod of 7 hours. The mixture was finally heated to 95 C. for 2 hoursunder 10 mm. pressure filtered hot. The product, filtered hot, amountedto 150 grams.

Formulated, applied and tested as described in the preceding examples,the product showed initial reflectance of 75 and a reflectance of 62after five washings.

EXAMPLE V A. Preparation of Polyol In the manner of the precedingexamples, 150 grams of 100 percent phosphoric acid was reacted with 550grams of distilled propylene oxide during a period of 5 hours. Anadditional 150 grams of propylene oxide was slowly added with agitationat 60 to 70 C. under nitrogen. The mixture was cooled to roomtemperature and later reheated to 70 C. An additional 150 grams ofpropylene oxide was added and the mixture was maintained at 80 C. for 6hours. The mixture was stripped at 80 C. under 10 mm. pressure to yield700 grams of polyol or 89 percent based on the materials charged. B.Reaction of Polyol with Phosphoric Anhydride A total of 190 grams of theproduct of Example V.A. and 42 grams of phosphoric anhydride werereacted for l 1 hours at temperatures up to 70 C. under a pressure of 10mm. The mixture was filtered to obtain the phosphate polyol product.

Formulated, applied and tested as described above, the reflectanceinitially was 75 and the reflectance after five washings was 58.

EXAMPLE VI A. Reaction of Polyol with Phosphoric Anhydride During aperiod of minutes, 42 grams of phosphoric anhydride was added to 190grams of vigorously stirred polyol prepared as described in ExampleI.B., all under an atmosphere of dry nitrogen and at a temperature of to30 C. Then 50 ml. of tetrahydrofuran was added slowly which greatlyreduced the viscosity of the mixture. Stirring was continued at 20 to 30C. for 20 hours and then the temperature was raised gradually to 66 C.where it was maintained for 5 hours. The resulting phosphated polyolproduct was vacuum filtered to clarify and to remove thetetrahydrofuran.

Formulated, applied and tested as described in Example the reflectanceinitially was 78 and after five washings was 63.

EXAMPLE VII A. Preparation of Polyol The polyol was prepared in a mannersimilar to the procedure described in Example LB. but using 100 percentpropylene oxide as the oxyallgylating agent. The

and good stirring. The product amounted to 217 grams or 94 percent oftheory.

C. Formulation Preparation 5 grams of the product form Example VILB. wasdissolved in 26 ml. of distilled water. Sodium hydroxide solution 10percent) was added to raise the pH to 4.0.

To the partly neutralized solution was added 2.5 grams of SR 525X, abath stabilizer, 12.5 grams of Perrnafresh LF (dimethylol dihydroxyethyleneurea), 1 gram of Polymel CC, a polyethylene emulsion softenerand 3 grams of magnesium chloride catalyst solution (35 percent). D.Formulation Application Two 5 inches by 5 inches test pieces of /35Dacron/cotton blended fabric were impregnated with the formulationprepared in Example VII.C. The swatches were squeezed to percent wetpick-up and hung on a line to dry for 2 hours. The impregnated swatcheswere cured at 160 C. for 3 minutes. E. Soil Release Evaluation One dropof oxidized olive oil was placed on each swatch and allowed to standfor4 hours forming a deep yellow stain about 1 inch in diameter. Thefabric was then washed for 15 minutes at 50 C. using 2 grams per literof Tide in a Tergotometer and then rinsed. The deep yellow stain wascompletely removed.

EXAMPLE VIII A. Reaction of Polyol with Phosphoric Acid percent) Amixture of 190 grams (0.42 moles) of the polyol prepared as described inExample VII.A. and 49 grams 0.5 moles of H PO added as 100 percentphosphoric acid was heated to C. under a pressure of 7 mm. for about 1hour.

B. Formulation Preparation A solution of 30 grams of the product ofExample VIILA. in 30 grams of distilled water was neutralized to a pH of6.5 by adding aqueous sodium bicarbonate solution. The formulation wascompleted by adding to the neutralized phosphated polyol the ingredientsof the textile finishing formulation as described in Example VII.C.

This formulation was applied to a Dacron/cotton fabric and evaluated asdescribed in Example VII substituting dirty motor oil for the oxidizedolive oil. After washing only a trace of the stain remained.

What is claimed is:

1. Method of preparing a phosphated polyol having hydroxyl number fromabout to and acid number from about 190 to 250 by (1) oxyalkylatingphosphoric acid at a temperature of from 0 to 100 C with an alkyleneoxide selected from the group consisting of propylene oxide and mixturescontaining at least 50 percent by weight of propylene oxide, balancealkylene oxides having two to four carbons, the molar 9 l ratio of saidoxides to said phosphoric acid being from 2. The product of the processof claim 1. 21110 1011 and heating the resulting p y at 3. Method asclaimed in claim 1 in which said oxide peratures from 30 to 150? C.under pressures not exis propylene oxide ceeding atmospheric with aphosphating agent selected from the group consisting of phosphoricanhydride and phosphoric acid containing at least 85 percent H PO themolar ratio of said polyol to each phosphorus atom in said phosphatingagent being from 0.5:! to 2.2: l.

4. Method as claimed in claim 1 in which said oxide is a mixture ofpropylene oxide and ethylene oxide in a weight ratio of at least about50/50.

P04 050 UNITED DIA'ILD ft! 1 DH 1 U1 runs v (5 69) CERTIFICATE OFCORRECTION- Patent No. 3 ,692 ,880 I Dated September 19, 1-972inventor-(s) Richard L. Doerr and Stephen Fuzesi It is certified thaterror appears in the above-identified patent and that said LettersPatent arehereby corrected as shown below:

Abstract, line 3, "particule-s" should read properties-,-

Column 6,' line 1, ,"to" should read -vallowed to Column 6,'line 53,"0t" should read --to--.

Column 6, line 13, "mounted" should read amounted- Signed and sealedthis 13thday of February 1973..

(SEAL) A .Attest:

EDWARD M. FLETCHER,JR. ROBERT GOTTSCHALK Attestlng Officer Commissionerof Patents

2. The product of the process of claim
 1. 3. Method as claimed in claim1 in which said oxide is propylene oxide.
 4. Method as claimed in claim1 in which said oxide is a mixture of propylene oxide and ethylene oxidein a weight ratio of at least about 50/50.